CN106311230B - Preparation method, catalyst and the application of silver catalyst for alkene epoxidation - Google Patents
Preparation method, catalyst and the application of silver catalyst for alkene epoxidation Download PDFInfo
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- CN106311230B CN106311230B CN201510374656.4A CN201510374656A CN106311230B CN 106311230 B CN106311230 B CN 106311230B CN 201510374656 A CN201510374656 A CN 201510374656A CN 106311230 B CN106311230 B CN 106311230B
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Abstract
The invention discloses a kind of preparation methods of silver catalyst for alkene epoxidation, the described method comprises the following steps: 1) providing alumina support；2) mixed solution of Ag-containing compound and organic amine is prepared, and impregnates the carrier；The solution for preparing rhenium-containing auxiliary agent, impregnates the carrier；3) mixture after the dipping in step 2) is separated by solid-liquid separation, obtains solid particle；4) solid particle in step 3) is dried, the drying carries out in the process for including at least two stages, and wherein the first stage is freeze-dried, and second stage carries out low temperature drying；5) solid particle after drying is activated, obtains the silver catalyst.The silver catalyst so prepared shows improved activity and selectivity when being used for ethylene epoxy ethane.The invention further relates to catalyst prepared in accordance with the present invention and its applications in ethylene production ethylene oxide.
Description
Technical field
The present invention relates to a kind of catalyst fields, and in particular to a kind of preparation side of the silver catalyst for alkene epoxidation
Method.The invention further relates to the silver catalyst as made from above-mentioned preparation method and its applications.
Background technique
Silver catalyst is to be commercially used for alkene epoxidation production epoxyalkane (such as ethylene epoxidizing production ethylene oxide)
Catalyst, reactivity worth index mainly includes activity, selectivity and stability.Epoxy second is produced with ethylene epoxidizing below
For alkane (EO), illustrate reactivity worth index.So-called activity refers to that process for ethylene oxide production reaches certain reaction load when institute
The reaction temperature needed.Reaction temperature is lower, and the activity of catalyst is higher.So-called selectivity refers to that ethylene is converted to epoxy in reaction
The ratio between molal quantity and the overall reaction molal quantity of ethylene of ethane.Under so-called stability is then expressed as activity and selectivity at any time
Reduction of speed rate, fall off rate is smaller, and the stability of catalyst is better.Epoxy will can be substantially used in the world according to the performance of catalyst
Ethane/ethylene glycol production silver catalyst is divided into three classes: the first kind is high activity silver catalyst, and this kind of catalyst activity is high, surely
Qualitative good, initial selectivity can achieve 80-82%, and service life is 2-5, be suitable for all EO/EG devices；Second class is
Highly selective silver catalyst, this kind of catalyst highest selectivity require CO in reaction gas up to 88% or more2Concentration control
1% hereinafter, being suitable for EO/EG process units newly-built, that space-time yield is relatively low；Third class is that intermediate selectivity silver is urged
Agent, for activity and selectivity between preceding two class, the highest of this kind of catalyst selectively can achieve 84-85%, it is desirable that
CO in reaction gas2Concentration controls below 3%.Above-mentioned catalyst choice is adjusted accordingly according to reaction burden requirement.
With petroleum resources scarcity and energy-efficient requirement, highly selective silver catalyst and intermediate selectivity silver catalyst increasingly
It is widely used in industrial production, to replace original high activity silver catalyst.
Silver catalyst generallys use infusion process preparation, and main includes preparing porous carrier and applying active component and auxiliary agent
The two processes on to carrier.
Drying is an indispensable step in catalyst preparation, is that a kind of purpose is that the process of absorption water is desorbed,
It is carried out usually in the air with higher temperature.It is dry usually to be carried out together with activation process in actual fabrication process.
Drying process described in the patent CN03806196.1 of Shell company is will to remove the catalyst precarsor of excess impregnation solution to exist
It is shaken and is continued 5.5 minutes for 250 DEG C in air stream.Heat treatment process described in the patent US5646087 of SD company is
Catalyst is realized by the heating furnace with seven heating zones.The temperature of heating zone is gradually increased to 400 DEG C from room temperature, from
After bringing-up section passes through, catalyst is cooled to using cooling section lower than 100 DEG C.It is retouched in the patent CN01126345.8 of Sinopec
The heat treatment process stated be purged 8 minutes in 260 DEG C of hot-air, then under a hydrogen atmosphere 400 DEG C handle 4 hours,
It is that impregnated carrier is heated to 5 minutes obtained catalyst in 400 DEG C of air stream in CN200510000464.3.These compared with
The drying and activation process carried out under high-temperature would generally be sent out inside the duct of porous carrier when dry due to capillarity
It the case where biomass migration and active component redistribution, generally can pore structure, mechanical strength and active component to catalyst
Larger impact is distributed with.
The present inventor provides a kind of preparation side of silver catalyst for alkene epoxidation by further investigation
Method can be improved the selectivity of silver catalyst by controlling preparation process.
Summary of the invention
In view of the situation of the above-mentioned prior art, the present inventor has carried out research extensively and profoundly in silver catalyst field, knot
Fruit discovery, the silver catalyst that the preparation method provided according to the present invention obtains, wherein the uniformity of active component and auxiliary agent distribution
Improved, the silver catalyst is obtaining improved work when such as ethylene epoxy ethane for catalyzing expoxidation of olefines
Property and selectivity.
Therefore it is an object of the present invention to provide a kind of preparation methods of silver catalyst for alkene epoxidation, especially
It is the preparation method of ethylene epoxidizing production ethylene oxide silver catalyst, which shows during epoxidation reaction
Good activity and selectivity is shown.
It is a further object of the present invention to provide a kind of silver catalysts obtained by above-mentioned preparation method.
Another object of the present invention is to provide application of the above-mentioned silver catalyst in ethylene production ethylene oxide.
These and other purposes, feature and advantage of the invention will become more to be illustrated after reading this specification.
According to an aspect of the invention, there is provided a kind of preparation by ethylene production ethylene oxide silver catalyst
Method the described method comprises the following steps:
1) alumina support is provided；
2) mixed solution of Ag-containing compound and organic amine is prepared, and impregnates the carrier；The solution of rhenium-containing auxiliary agent is prepared,
Impregnate the carrier；
3) mixture after the dipping in step 2) is separated by solid-liquid separation, obtains solid particle；
4) solid particle in step 3) being dried, the drying carries out in the process for including at least two stages,
Wherein the first stage is freeze-dried, and second stage carries out low temperature drying；
5) solid particle after drying is activated, obtains the silver catalyst.
The method provided according to the present invention in drying in the first stage, can slough 90% or so water and volatile
Component；In the drying of second stage, remaining water and volatile components are removed.Entire drying process at a lower temperature into
Row, avoids high temperature influence caused by Active components distribution.
The method provided according to the present invention makes vapor and volatile components directly distil out under conditions of close to vacuum
Come, and active component and auxiliary component remain in carrier, then material transport and solute concentration phenomena will not occur；Lower
At a temperature of catalyst is dried, avoid the adverse effect that high temperature drying generates Active components distribution, so as to improve
Catalyst performance.
The drying of a specific embodiment according to the method for the present invention, the first stage is freeze-drying, to make water
Steam and volatile components, which directly distil, to be come out, and active component and auxiliary component remain in carrier, then substance will not occur
Migration and solute concentration phenomena.As long as pressure and temperature used in the first stage can make substance be in freeze-drying state i.e.
It can.In a specific example, the first stage at 0.01kPa to less than 0.1MPa, such as 0.01-50kPa, such as
0.01-10kPa, such as 0.01-5kPa；It is preferred that 0.01-1.0kPa, such as 0.01-0.9kPa, such as 0.01-0.8kPa, such as 0.01-
0.7kPa, as carried out under 0.01-0.6kPa.It is highly preferred that the first stage carries out at 0.01-0.5kPa, such as 0.01-
0.4kPa, such as 0.01-0.3kPa；It is most preferably carried out at 0.01-0.2kPa, such as 0.01-0.16kPa, such as 0.03-0.16kPa,
Such as 0.01-0.03kPa.In another specific example, the first stage at -75 DEG C to -1 DEG C, such as -75 to -5 DEG C
Under, at -60 to -10 DEG C, preferably -50 DEG C Dao -15 DEG C, at -20 DEG C to -50 DEG C, as carried out at -30 DEG C to -50 DEG C.Upper
It states under temperature and/or pressure, available preferable effect, is conducive to being uniformly distributed for active component and adjuvant component, obtain
The balances of process costs and catalyst performance.
Another specific embodiment according to the method for the present invention, the low temperature of the second stage are 0-100 DEG C, preferably 0
To less than 100 DEG C；And/or the drying of second stage carries out under reduced pressure.Second-order is carried out at lower temperature and/or decompression
The drying of section is conducive to being uniformly distributed for active component and adjuvant component.In a specific example, the second stage
Low temperature is 1-80 DEG C, such as 5-80 DEG C, such as 10-80 DEG C, and such as 10-70 DEG C, such as 10-60 DEG C；It is preferred that 10-50 DEG C, more preferable 10-40
℃.In another specific example, the drying of the second stage is at 0.01kPa to less than 0.1MPa, such as 0.01-
90kPa, such as 0.01-80kPa, such as 0.01-70kPa, such as 0.01-60kPa, under 0.01-50kPa；It is preferred that 0.01-47.0kPa, such as
0.01-40kPa, such as 0.01-30kPa, such as 0.01-20kPa；Under more preferable 0.015-12.0kPa, such as 0.2-12.0kPa, such as 2-
12kPa, such as 4-12kPa, as carried out under 7-12kPa.At above-mentioned temperature and/or pressure, available preferable effect, favorably
In being uniformly distributed for active component and adjuvant component, the balance of process costs and catalyst performance is achieved.
Another specific embodiment of method according to the present invention, the dry of the first stage carry out 0.1-24h,
It is preferred that 5-20h, more preferable 8-15h.The dry of the second stage carries out 0.1-24h, preferably 1-20h, more preferable 2-12h.?
In the above-mentioned time, is conducive to obtain preferable drying effect in a relatively short period of time, achieves the balance of Cost And Performance.
In the method that the present invention prepares silver catalyst, alumina support is impregnated with mixed solution.The aluminium oxide
Carrier is porous alpha-alumina supports.The porous alpha-alumina supports have the feature that Alpha-alumina content >=90wt%,
The specific surface area of BET method measurement is 0.8-3.0m2/ g, Kong Rongwei 0.3-0.8ml/g, water absorption rate 30-70%, and crushing are strong
Degree is 50-180N/.
In the present invention, the specific surface area of carrier is measured using nitrogen physisorption BET method, and Kong Rong is using pressure mercury method
Measurement, water absorption rate are measured by densimetry, and side pressure strength uses DL II type intelligence detector for strength of particles, choose support samples,
It is averaged to obtain after measuring radial crushing strength.
The alumina support that the present invention uses can be provided by the method containing following steps.
(1) preparation has the mixture formed as follows:
It a) is the three water α-Al of 50-500 purpose of 5-90% weight based on solid mixture total weight2O3；
B) it is greater than the one water Al of vacation of 200 mesh based on the granularity that solid mixture total weight is 5-70% weight2O3；
C) based on solid mixture total weight be 0-5% weight can after-flame lubriation material；
It d) is the fluxing agent of 0.01-5.0% weight based on solid mixture total weight；
It e) is the fluoride-mineralization agent of 0.01-5.0% weight based on solid mixture total weight；
It f) is the heavy alkaline earth metal compound of 0-5.0% weight based on solid mixture total weight；
Component a)-f) the sum of content be 100% weight；
G) total weight based on above solid component a)-f) is the binder of 25-60% weight；And
H) suitable water；
(2) mixture obtained in step (1) is uniformly mixed and is formed, obtain formed body；And
(3) formed body obtained in drying steps (2), then porous α-Al is made in roasting at 1200-1500 DEG C2O3
Carrier.
In support preparation method of the invention, three water α-Al have been used2O3With one water Al of vacation2O3As raw material.Used three
Water α-Al2O3It can completely or partially be replaced by Alpha-alumina and the powder of transition aluminas, but its total amount is constant, i.e., based on solid
Body total weight of the mixture is 5-90% weight.
In support preparation method of the invention, can after-flame lubriation material addition be on the one hand to manufacture macropore, make
Carrier has suitable pore structure and specific surface, while playing the role of lubrication, makes carrier convenient for molding, such as extrusion molding.Institute
State can after-flame lubriation material include that petroleum coke, carbon dust, graphite, polyethylene, vaseline etc. are one such or a variety of, preferred petroleum
Burnt, graphite or vaseline.
In support preparation method of the invention, fluxing agent is added to make carrier under low maturing temperature with good
Good intensity.The example of fluxing agent includes one of magnesium-containing compound, such as magnesia, magnesium sulfate, magnesium nitrate and magnesium carbonate
Or it is a variety of.
In support preparation method of the invention, the fluoride-mineralization agent of selection include hydrogen fluoride, ammonium fluoride, aluminum fluoride,
Or mixtures thereof magnesium fluoride, ice crystal etc., its role is to the transformation of crystal of accelerated oxidation aluminium, and reduce 0.1 μm below thin
Hole.
In support preparation method of the invention, the heavy alkaline earth metal compound optionally added includes the oxygen of strontium and/or barium
Compound, sulfate, acetate, nitrate and oxalates etc., its role is to improve to carrier.
One water Al of vacation in support preparation method of the invention, by the way that binder is added, in it and mixture2O3It generates
Each component is bonded together by Aluminum sol, becomes extrudable molding paste.Binder used includes acid, such as nitric acid, first
Acid, acetic acid, propionic acid and hydrochloric acid etc., or by one water Al of vacation2O3It is replaced with acid with Aluminum sol.When using acid as binder, preferably
Be aqueous solution of nitric acid, wherein nitric acid and water weight ratio be 1:1.25-10, preferably 1:2-4.
Aqueous 10% weight can be dried to after gained paste extrusion molding hereinafter, support shapes can be annular, it is spherical,
Cylindricality, more void column shapes or other shapes.Drying temperature is 80-120 DEG C, and drying time controls small in 1-24 according to moisture content
When.
Formed body after drying roasts 2-6 hours at 1200-1500 DEG C, keeps aluminium oxide substantially all, such as 90%
It is converted into α-Al above2O3.Thus porous α-Al is obtained2O3Carrier.
In order to form the mixed solution of oxide impregnation alumina supporter, organic amine and Ag-containing compound therein form silver-colored amine complexing
Solution.Organic amine compound used in the present invention can be suitable for any organic amine compound in the art, as long as this has
Machine amine compounds can form argent-amine complex with silver compound.For the purpose of the present invention, pyridine, butylamine, second can be used
Diamines, 1, the mixture of or mixtures thereof 3 propane diamine, ethanol amine, preferably ethylenediamine and ethanol amine.Argentiferous used in the present invention
Compound can be any Ag-containing compound in the art.It is, for example, possible to use one in silver oxalate, silver oxide and silver nitrate
Kind is a variety of, preferably silver nitrate and/or silver oxalate.The dosage of silver compound should make the silver catalyst in the mixed solution
In, based on the element, silver-colored content is 1-30wt%, preferably 5-26wt%, the total weight based on silver catalyst.Argentamine liquid is matched
Process processed discharges a large amount of heat, if temperature is excessively high, the argent-amine complex of generation easily decomposes the silver oxide for generating indissoluble
(Ag2O), influence maceration extract quality and finally influence the performance of catalyst；Temperature is too low, and the solution rate of silver compound is excessively slow.
Therefore, the temperature controlled in argentamine liquid process for preparation is just very necessary, and the present invention preferably should when preparing argentamine liquid
The temperature of solution should keep below 30 DEG C, preferably 5-20 DEG C.
According to another embodiment of the invention, the rhenium auxiliary agent can be the oxide, perrhenic acid or perrhenate of rhenium,
It is either aforementioned to contain two or more any mixtures, preferably ammonium perrhenate and/or perrhenic acid caesium in rhenium compound.It is preferred that
The dosage on ground, the rhenium auxiliary agent should make the content 1-1000ppm of rhenium element in the silver catalyst, preferably 100-
800ppm, the total weight based on silver catalyst.With Ag-containing compound and can have with the solution impregnating carrier of rhenium-containing auxiliary agent
The mixed solution impregnated carrier of machine amine carries out before, after or at the same time.When simultaneously carry out when, the solution of rhenium-containing auxiliary agent with contain patina
The mixed solution for closing object and organic amine can merge use.
In another specific example of the invention, the carrier is impregnated with the solution of the coassist agent comprising rhenium auxiliary agent.Institute
State the coassist agent comprising rhenium auxiliary agent solution impregnate the carrier can before impregnating the carrier with the solution of rhenium-containing auxiliary agent,
It carries out later or simultaneously.When carrying out simultaneously, two kinds of solution can merge use.The coassist agent of the rhenium auxiliary agent used can be member
The mixture of the compound of any transition metal or several transistion metal compounds in plain periodic table, is preferably selected from the following group
One or more: VI B race, VII B group 4 transition metal element oxyacid and its salt, be more preferably selected from chromium, molybdenum, tungsten and dilute
The oxyacid and its salt of earth metal；Such as the salt of wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate etc. and rare earth metal, such as sulfuric acid height
Cerium.Preferably, the dosage of the coassist agent of the rhenium auxiliary agent should make the content 1- of coassist agent element in the silver catalyst
500ppm, more preferable 1-300ppm, the total weight based on silver catalyst.
Another specific embodiment according to the present invention is soaked with the solution of alkali metal containing auxiliary agent and/or base earth metal promoter
Carrier described in stain.The solution of the alkali metal containing auxiliary agent and/or base earth metal promoter impregnates the carrier can mix with described
Solution impregnating carrier is closed to carry out before, after or at the same time.When carrying out simultaneously, two kinds of solution can merge use.It is used
Alkali metal promoter can be the compound of lithium, sodium, potassium, rubidium or caesium, such as their nitrate, sulfate or hydroxide, or
It is any two or more of combinations of aforesaid compound, preferably sulfuric acid caesium and/or cesium nitrate.Preferably, the alkali metal helps
The dosage of agent should make the content 5-2000ppm of alkali metal element in the silver catalyst, preferably 10-1500ppm, based on silver
The total weight of catalyst.
The base earth metal promoter can be the compound of magnesium, calcium, strontium or barium, such as their oxide, sulfate, nitre
Any two or more of combinations of hydrochlorate, oxalates or acetate or aforesaid compound, the preferably change of barium and/or strontium
Close object, more preferable barium acetate and/or strontium acetate.Preferably, the dosage of the base earth metal promoter should make in the silver catalyst
The content of alkali earth metal is 1-2000ppm, more preferably 10-1500ppm, the total weight based on silver catalyst.
In the method that the present invention prepares silver catalyst, the solid particle (catalyst precarsor) after drying is carried out at activation
Reason is such as activated in nitrogen oxygen atmosphere of the air or oxygen content no more than 21 volume %, activation temperature 180-700
DEG C, preferably 200-500 DEG C, activation time is 1-120 minutes, preferably 2-60 minutes.
The method provided according to the present invention, is dried at a lower temperature, and the wet carrier after dipping is first cooled down
It is frozen into solid, so that vapor and volatile components is directly distilled under conditions of close to vacuum and comes out, and active component
It is remained in carrier with auxiliary component, then material transport and solute concentration phenomena will not occur；At a lower temperature to catalysis
Agent is dried, and avoids the adverse effect that high temperature drying generates Active components distribution, improves catalyst performance.Pass through this
The silver catalyst for the method preparation that invention provides, has good activity and selectivity.
According to another aspect of the present invention, a kind of silver catalyst for alkene epoxidation is provided, by upper
Method preparation is stated, the silver catalyst includes α-Al2O3Carrier and the component I deposited thereon) 1-30wt%, preferably 5-
The silver-colored active component and III in terms of silver element of 26wt%) 1-1000ppm, the rhenium element of preferably 100-800ppm；Based on silver
The total weight of catalyst.
A specific embodiment of the silver catalyst, the total weight based on silver catalyst, the silver are urged according to the present invention
Also include in agent: II) 5-2000ppm, the preferably alkali metal element of 10-1500ppm；Optional IV) alkali earth metal, when
When alkaline including earth metal element, in an amount of from 1-2000ppm, preferably 10-1500ppm；And optional V) rhenium coassist agent element,
When the coassist agent element of rhenium-containing, in an amount of from 1-500ppm, preferably 1-300ppm.
Silver catalyst according to the present invention, it is described to be optional that finger contain or be free of.For example, optional alkali
Earth metal element, alkali earth metal can also be free of with alkaline including earth metal element by referring to.Silver catalyst provided by the invention
With good activity and selectivity.
According to another aspect of the present invention, the silver catalyst or above-mentioned silver for additionally providing above method preparation are catalyzed
Application of the agent in alkene epoxidation.Wherein, the alkene optimal ethylene.The silver catalyst of above method preparation has well
Performance, activity and selectivity with higher, be particularly suitable for ethylene epoxidizing production ethylene oxide reaction.
Specific embodiment
Present invention combination the following examples are described further, but the scope of the invention is not limited to these implementations
Example.
Catalyst performance evaluation
Various silver catalysts of the invention test it with laboratory microreactor (hereinafter referred to as " micro- anti-") evaluating apparatus
Activity and selectivity in ethylene production reacting ethylene oxide.The reactor that microreactor evaluating apparatus uses is interior
The stainless steel tube of diameter 4mm, reactor are placed in heating mantle.The admission space of catalyst is 1ml, and there is inert filler in lower part, makes to urge
Agent bed is located at the flat-temperature zone of heating mantle.The composition of the reaction gas of Reactor inlet are as follows: ethylene (C2H4), 28.0 ±
1.0mol%；Oxygen (O2), 7.4 ± 0.2mol%；Carbon dioxide (CO2), < 8.0mol%；Cause steady gas (N2), surplus；Inhibitor
Dichloroethanes (mol%), 0.1-2.0ppm.
Test reaction condition is as follows: reaction pressure 2.1MPa, air speed 5000/h, reactor outlet EO concentration 2.50%.It comments
Space-time yield used in valence catalyst activity is 246kgEO/lm3Cat./h.Connect after stably reaching the test reaction condition
Continuous measurement reactor enters, exit gas forms.Measurement result calculates selectivity after carrying out volume contraction correction as follows:
Wherein Δ EO is, the Δ CO poor with inlet gas ethylene oxide concentration that work off one's feeling vent one's spleen2It is to work off one's feeling vent one's spleen and titanium dioxide in inlet gas
Concentration of carbon is poor, takes test result of the average of 10 groups or more test datas as the same day.
Support preparation method is as follows in following embodiment and comparative example: by three water α-Al of 50-500 purpose2O3336g is greater than
The one water Al of vacation of 200 mesh2O375g, mineralizer 7.0g, alkali salt 1.0g and vaseline 10.0g, are put into blender and mix
Uniformly, it is transferred to kneader, dust technology (nitric acid: water=1:3) 90ml is added, is kneaded into extrudable molding paste.It is extruded into
Type is outer diameter 8.0mm, long 6.0mm, long 6.0mm, and the five hole columns of internal diameter 1.0mm are dried overnight at 120 DEG C.It will dry
Product is put into top-hat kiln, is increased between 1200-1500 DEG C through 30 hours or so from room temperature, constant temperature 2 hours, obtains white α-
Al2O3Support samples.Carrier property is as follows: α-Al2O3Content is 90 weight %, and the specific surface area of BET method measurement is 1.1m2/ g,
Kong Rongwei 0.54ml/g, water absorption rate 54% and crushing strength are 83N/.
Comparative example 1
100g silver nitrate is taken to be dissolved in 110ml deionized water.47g ammonium oxalate is taken to be dissolved in 50 DEG C of 35ml of deionized water.
Above two solution is mixed with vigorous stirring, generates white silver oxalate precipitate.Aging 30 minutes or more, deionization was used in filtering
Water washing is precipitated to no nitrate ion.Filter cake argentiferous about 60%, aqueous about 15%.
Add 32g ethylenediamine, 11g ethanol amine, 38g deionized water in the glass flask with stirring.Made from lower of stirring
Silver oxalate paste is slowly added into mixed liquor, and temperature is maintained at 30 DEG C hereinafter, dissolving silver oxalate all.Wherein silver oxalate
Additional amount accounts for the 24% of maceration extract gross mass in terms of silver.Then 0.39g cesium sulfate, 0.38g strontium acetate and 0.19g perrhenic acid is added
Ammonium, then plus deionized water so that solution gross mass is reached 200g, it is stand-by that maceration extract is made.
It takes the above-mentioned support samples of 100g to be put into the container that can be vacuumized, is evacuated to vacuum degree greater than 0.01MPa, is added
The above maceration extract, after submerging carrier and being kept for 30 minutes, leaching removes extra solution.Sky of the carrier at 300 DEG C after dipping
It is heated 5 minutes in air-flow, it is cooling, that is, ethylene oxide silver catalyst is made, is referred to as comparative catalyst 1.
The catalytic performance data that silver catalyst is made are shown in Table 1.
Comparative example 2
With comparative example 1, the difference is that being first heated to 80 DEG C after the carrier leaching after dipping removes redundant solution
Air stream in dry 3 minutes, then activate 5 minutes in the air stream for being heated to 300 DEG C, it is cooling, that is, ethylene oxide is made and uses
Silver catalyst is referred to as comparative catalyst 2.
The catalytic performance data that silver catalyst is made are shown in Table 1.
Embodiment 1
With comparative example 1, the difference is that after the carrier leaching after dipping removes redundant solution, first -50 DEG C,
Dry 15h under conditions of 0.01kPa, then dry 12h under conditions of 10 DEG C, 0.02kPa, which can be in vacuum refrigeration
It is carried out in the similar devices such as drying machine.Carrier after drying heats 5 minutes in 300 DEG C of air stream again, cooling, that is, ring is made
Oxidative ethane silver catalyst is referred to as invention catalyst 1.
Embodiment 2
With comparative example 1, the difference is that after the carrier leaching after dipping removes redundant solution, first -40 DEG C,
Dry 15h under conditions of 0.01kPa, then dry 2h under conditions of 50 DEG C, 12kPa.Carrier after drying is again in 300 DEG C of sky
Heat-activated 5 minutes in air-flow, it is cooling, that is, ethylene oxide silver catalyst is made, is referred to as invention catalyst 2.
Embodiment 3
With comparative example 1, the difference is that after the carrier leaching after dipping removes redundant solution, first -30 DEG C,
Dry 10h under conditions of 0.03kPa, then dry 5h under conditions of 40 DEG C, 7kPa.Carrier after drying is again in 300 DEG C of sky
Heat-activated 5 minutes in air-flow, it is cooling, that is, ethylene oxide silver catalyst is made, is referred to as invention catalyst 3.
Embodiment 4
With comparative example 1, the difference is that after the carrier leaching after dipping removes redundant solution, first -15 DEG C,
Dry 8h under conditions of 0.16kPa, then dry 7h under conditions of 30 DEG C, 4kPa.Carrier after drying is again in 300 DEG C of air
Heat-activated 5 minutes in stream, it is cooling, that is, ethylene oxide silver catalyst is made, is referred to as invention catalyst 4.
Embodiment 5
With comparative example 1, the difference is that after the carrier leaching after dipping removes redundant solution, first -20 DEG C,
Dry 12h under conditions of 0.1kPa, then dry 10h under conditions of 20 DEG C, 2kPa.Carrier after drying is again in 300 DEG C of sky
Heat-activated 5 minutes in air-flow, it is cooling, that is, ethylene oxide silver catalyst is made, is referred to as invention catalyst 5.
Embodiment 6
With comparative example 1, the difference is that after the carrier leaching after dipping removes redundant solution, first -45 DEG C,
Dry 15h under conditions of 0.01kPa, then dry 12h under conditions of 40 DEG C, 7kPa.Carrier after drying is again in 300 DEG C of sky
Heat-activated 5 minutes in air-flow, it is cooling, that is, ethylene oxide silver catalyst is made, is referred to as invention catalyst 6.
The catalytic performance data that silver catalyst is made are shown in Table 1.
Table 1
| Reaction temperature/DEG C | Selectivity/% | |
| Comparative example 1 | 230 | 83.52 |
| Comparative example 2 | 231 | 83.38 |
| Embodiment 1 | 226 | 83.90 |
| Embodiment 2 | 227 | 83.98 |
| Embodiment 3 | 228 | 84.02 |
| Embodiment 4 | 229 | 83.73 |
| Embodiment 5 | 228 | 83.79 |
| Embodiment 6 | 225 | 83.88 |
The data from table 1 are it is known that embodiment is compared with comparative example, and manufactured silver is urged according to the method provided by the invention
Reaction of the agent for ethylene production ethylene oxide, has lower reaction temperature, this means that urging in the present invention
Agent activity with higher；Meanwhile the catalyst provided according to the present invention selectivity also with higher.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (26)
1. a kind of preparation method of the silver catalyst for alkene epoxidation, the described method comprises the following steps:
1) alumina support is provided；
2) mixed solution of Ag-containing compound and organic amine is prepared, and impregnates the carrier；Prepare the solution of rhenium-containing auxiliary agent, dipping
The carrier；
3) mixture after the dipping in step 2 is separated by solid-liquid separation, obtains solid particle；
4) solid particle in step 3) being dried, the drying carries out in the process for including at least two stages, wherein
First stage is freeze-dried, and second stage carries out low temperature drying；
5) solid particle after drying is activated, obtains the silver catalyst；
The first stage dry 10-15h under the conditions of 0.01-0.1kPa, -50 DEG C to -20 DEG C；
The second stage dry 0.1-24h under the conditions of 0.01kPa to less than 0.1MPa, 1-80 DEG C.
2. the method according to claim 1, wherein the low temperature of the second stage is 10-50 DEG C；And/or institute
The drying for stating second stage is carried out at 0.01-47.0kPa；And/or the dry of the second stage carries out 1-20h.
3. the method according to claim 1, wherein the low temperature of the second stage is 10-40 DEG C；And/or institute
The drying for stating second stage is carried out at 0.015-12.0kPa；And/or the dry of the second stage carries out 2-12h.
4. the method according to claim 1, wherein described in the dosage of silver compound should make in the mixed solution
The content of silver element is 1-30wt%, the total weight based on silver catalyst in silver catalyst.
5. according to the method described in claim 4, it is characterized in that, described in the dosage of silver compound should make in the mixed solution
The content of silver element is 5-26wt%, the total weight based on silver catalyst in silver catalyst.
6. the method according to claim 1, wherein the solution impregnating carrier with rhenium-containing auxiliary agent is with argentiferous
The mixed solution impregnated carrier of compound and organic amine carries out before, after or at the same time；When carrying out simultaneously, the rhenium-containing auxiliary agent
Solution merge use with the mixed solution of Ag-containing compound and organic amine.
7. according to the method described in claim 6, it is characterized in that, the rhenium auxiliary agent is selected from oxide, perrhenic acid, the high rhenium of rhenium
At least one of sour caesium, methyl rhenium trioxide and ammonium perrhenate.
8. according to the method described in claim 6, it is characterized in that, the dosage of the rhenium auxiliary agent should make rhenium in the silver catalyst
The content of element is 1-1000ppm, the total weight based on silver catalyst.
9. according to the method described in claim 8, it is characterized in that, the dosage of the rhenium auxiliary agent should make rhenium in the silver catalyst
The content of element is 100-800ppm, the total weight based on silver catalyst.
10. the method according to claim 1, wherein described in the solution of the coassist agent comprising rhenium auxiliary agent dipping
Carrier.
11. according to the method described in claim 10, it is characterized in that, the coassist agent of the rhenium auxiliary agent is selected from VI B race, VII B
The oxyacid and its salt of group 4 transition metal element.
12. according to the method for claim 11, which is characterized in that the coassist agent of the rhenium auxiliary agent is selected from chromium, molybdenum, tungsten and dilute
The oxyacid and its salt of earth metal.
13. according to the method for claim 11, which is characterized in that the dosage of the coassist agent of the rhenium auxiliary agent should make the silver
The content of coassist agent element is 1-500ppm, the total weight based on silver catalyst in catalyst.
14. according to the method for claim 13, which is characterized in that the dosage of the coassist agent of the rhenium auxiliary agent should make the silver
The content of coassist agent element is 1-300ppm, the total weight based on silver catalyst in catalyst.
15. the method according to claim 1, wherein molten with alkali metal containing auxiliary agent and/or base earth metal promoter
Liquid impregnates the carrier.
16. according to the method for claim 15, which is characterized in that the dosage of the alkali metal promoter should make the silver catalysis
The content of alkali metal element is 5-2000ppm, the total weight based on silver catalyst in agent.
17. according to the method for claim 16, which is characterized in that the dosage of the alkali metal promoter should make the silver catalysis
The content of alkali metal element is 10-1500ppm, the total weight based on silver catalyst in agent.
18. according to the method for claim 15, which is characterized in that the dosage of the base earth metal promoter should be such that the silver urges
The content of alkali earth metal is 1-2000ppm, the total weight based on silver catalyst in agent.
19. according to the method for claim 18, which is characterized in that the dosage of the base earth metal promoter should be such that the silver urges
The content of alkali earth metal is 10-1500ppm, the total weight based on silver catalyst in agent.
20. method described in any one of -19 according to claim 1, which is characterized in that alpha-oxidation in the alumina support
Aluminium content >=90wt %, the specific surface area of BET method measurement are 0.8-3.0m2/ g, Kong Rongwei 0.3-0.8mL/g, water absorption rate 30-
70% and crushing strength be 50-180N/.
21. a kind of silver catalyst for alkene epoxidation is prepared by any one of claim 1-20 the method,
The silver catalyst includes α-Al2O3Carrier and the component I deposited thereon) 1-30wt% the silver-colored active group in terms of silver element
Point and III) 1-1000ppm rhenium element；Total weight based on silver catalyst.
22. silver catalyst according to claim 21, which is characterized in that the silver catalyst includes α-Al2O3Carrier and
The component I deposited thereon) 5-26wt% the silver-colored active component and III in terms of silver element) 100-800ppm rhenium element；It is based on
The total weight of silver catalyst.
23. silver catalyst according to claim 21, which is characterized in that the total weight based on silver catalyst, the silver are urged
Include in agent: II) alkali metal element of 5-2000ppm；Optional IV) alkali earth metal, when alkaline including earth metal element,
In an amount of from 1-2000ppm；And optional V) rhenium coassist agent element, when the coassist agent element of rhenium-containing, in an amount of from 1-
500ppm。
24. silver catalyst according to claim 23, which is characterized in that the total weight based on silver catalyst, the silver are urged
Include in agent: II) alkali metal element of 10-1500ppm；Optional IV) alkali earth metal, when alkaline including earth metal element
When, in an amount of from 10-1500ppm；And optional V) rhenium coassist agent element, when the coassist agent element of rhenium-containing, in an amount of from 1-
300ppm。
25. any in the silver catalyst or claim 21-24 of the preparation of any one of -20 the methods according to claim 1
Application of the silver catalyst in alkene epoxidation described in.
26. application according to claim 25, which is characterized in that the alkene is ethylene.
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| CN110605116B (en) * | 2018-06-15 | 2022-07-12 | 中国石油化工股份有限公司 | Silver impregnation liquid and silver catalyst for producing ethylene oxide by ethylene epoxidation and preparation method thereof |
| CN111905733B (en) * | 2019-05-09 | 2022-10-18 | 中国石油化工股份有限公司 | Method for activating silver catalyst and application |
| CN115382525B (en) * | 2021-05-24 | 2024-05-10 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN113843549A (en) * | 2021-11-18 | 2021-12-28 | 深圳先进电子材料国际创新研究院 | Silver soldering paste sintering aid and preparation method and application thereof |
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| US5801259A (en) * | 1996-04-30 | 1998-09-01 | Shell Oil Company | Ethylene oxide catalyst and process |
| CN1223901A (en) * | 1997-12-16 | 1999-07-28 | 株式会社日本触媒 | Silver catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide |
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| CN102921475A (en) * | 2012-08-03 | 2013-02-13 | 北京化工大学 | Sheet-shaped or polyhedron-shaped supported silver catalyst and preparation method thereof |
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| US5801259A (en) * | 1996-04-30 | 1998-09-01 | Shell Oil Company | Ethylene oxide catalyst and process |
| CN1223901A (en) * | 1997-12-16 | 1999-07-28 | 株式会社日本触媒 | Silver catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide |
| CN1467028A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing vinyl epoxide argentum catalyst |
| CN102145285A (en) * | 2010-02-05 | 2011-08-10 | 中国石油化工股份有限公司 | Carrier of silver catalyst for producing epoxy ethane, preparation method and application of carrier of silver catalyst |
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